CN104774474B - A kind of halogen-free flameproof enhancing add-on type liquid silicon rubber and preparation method thereof - Google Patents
A kind of halogen-free flameproof enhancing add-on type liquid silicon rubber and preparation method thereof Download PDFInfo
- Publication number
- CN104774474B CN104774474B CN201510007060.0A CN201510007060A CN104774474B CN 104774474 B CN104774474 B CN 104774474B CN 201510007060 A CN201510007060 A CN 201510007060A CN 104774474 B CN104774474 B CN 104774474B
- Authority
- CN
- China
- Prior art keywords
- silicon rubber
- add
- type liquid
- liquid silicon
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 71
- 239000007788 liquid Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- 239000001257 hydrogen Substances 0.000 claims abstract description 53
- 229920002545 silicone oil Polymers 0.000 claims abstract description 40
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 32
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 21
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 21
- 239000003063 flame retardant Substances 0.000 claims abstract description 20
- 238000009830 intercalation Methods 0.000 claims abstract description 16
- 230000002687 intercalation Effects 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 acetenyl Chemical group 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000000622 irritating effect Effects 0.000 abstract description 2
- 230000001473 noxious effect Effects 0.000 abstract description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920000260 silastic Polymers 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Abstract
The invention discloses a kind of halogen-free flameproof enhancing add-on type liquid silicon rubber and preparation method thereof.The composition of raw materials component of the preparation method is：100 parts of vinyl silicone oil, 30~60 parts of white carbon, 1~10 part of containing hydrogen silicone oil, 2~10 parts of fire retardant, 10~40ppm of platinum catalyst parts, 0.004~0.03 part of 1 acetenyl, 1 cyclohexanol.Fire retardant is hindered amine intercalation modifying phosphoric acid hydrogen zirconium.Not only mechanical property is good for add-on type liquid silicon rubber of the invention, and in excellent fireproof performance, and combustion process, will not produce noxious material and irritative gas, meets the requirement of environmental protection, can be widely used for the fields such as space flight and aviation, electronic apparatus and electric power.
Description
Technical field
The present invention relates to organosilicon macromolecule material flame retardant area, and in particular to a kind of halogen-free flameproof strengthens add-on type liquid
Silicon rubber and preparation method thereof.
Technical background
Silicon rubber has the performances such as excellent high-low temperature resistant, weather-proof, electrical insulating property, resistant to chemical etching and physiological inertia, extensively
The general every field for being applied to national economy.Wherein add-on type liquid silicon rubber due to process is simple, and in sulfidation not
Accessory substance is produced, shrinkage factor is low, has broad application prospects.But add-on type liquid silicon rubber is the same with usual silicone rubber, point
All contain substantial amounts of C, H in subchain, meeting naked light can glow, which greatly limits it in space flight and aviation, electronic apparatus and electricity
Power etc. carries out fire-retardant research to add-on type liquid silicon rubber and just seems particularly with compared with the application in high fire-retardance requirement field
It is urgent and important.
There is more research to halogen-free flameproof peroxide curable silicon rubber and condensed type silicon rubber at present.Its Patent
CN102876045 discloses one kind using magnalium hydrotalcite, APP and magnesium hydroxide compounding as fire retardant, effectively improves
The fire resistance of condensed type silicon rubber, but fire retardant addition is up to 70~130 parts, the mechanical property of silicon rubber can be greatly reduced
Energy.Patent CN102010599 is reported with Quadrafos, polyalcohol and melamine as Intumscent Flame Retardant System, with silicones and its
He compounds filler, and the peroxide curable silicon rubber with excellent fire-retardancy, but expansion type flame retardant and silicon rubber is obtained
Poor compatibility, the mechanical property and processing characteristics of meeting serious deterioration silicon rubber.Patent CN102660123 is reported poly- metal
Organic siloxane as fire retardant, and silicon rubber, gas-phase silica, 2,5- dimethyl -2,5- bis(t-butylperoxy)s hexane and
Constitution controller is compounded, and is obtained the peroxide curable silicon rubber of high flame resistance, but is had that addition is big, cost is high etc. and lacked
Point.
Add-on type liquid silicon rubber usually using compound containing platinum as catalyst, but organic matter containing elements such as N, P, S,
Ionic compound containing heavy metals such as Sn, Pb, Hg, Bi, As or the unsaturated compoundses containing alkynyl are all easily caused platinum catalyst
Lose activity, add-on type liquid silicon rubber is smoothly vulcanized (the platinum catalyst progress aerospace materials in silicone industry
Material technique, 1999,3:19), which greatly limits the development for add-on type liquid silicon rubber fire retardant.At present using most
It is to add one or more the mixture in aluminium hydroxide, magnesium hydroxide or Firebrake ZB to obtain good fire-retardant effect
Really.But obtain satisfied fire resistance, it usually needs addition more than 50wt%, this severe exacerbation add-on type liquid silicon rubber that is bound to
The processing characteristics and mechanical property of glue.Therefore a kind of add-on type liquid silicon rubber with excellent mechanical performance and fire resistance is studied
Glue, tool is of great significance.
The content of the invention
Shortcoming it is an object of the invention to be directed to existing fire-retardant add-on type liquid silicon rubber, there is provided a kind of fire resistance and
The halogen-free flameproof add-on type liquid silicon rubber of good mechanical performance.
Strengthen the preparation side of add-on type liquid silicon rubber the present invention also aims to provide a kind of described halogen-free flameproof
Method.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of halogen-free flameproof strengthens the preparation method of add-on type liquid silicon rubber, comprises the following steps：
55wt%~the 95wt% and gas-phase silica of raw material medium vinyl silicone oil are mixed in vacuum kneader, 25
1~3h is kneaded at~35 DEG C, 140~180 DEG C of temperature of charge is heated to and is continued to knead 1~2h, then vacuum kneading 0.5~1h, it is cold
But grind afterwards, obtain component A；
B, by fire retardant ultrasonic disperse in the first solvent, ultrasonic time be 0.1~2h, add formula in remaining second
Alkenyl silicone oil, stirs 0.5~6h at 25~35 DEG C, and revolving removes the first solvent, obtains component B；First solvent is first
Benzene, benzene, dimethyl ether, methyl ethyl ketone or carbon tetrachloride；
C, by component A, component B, containing hydrogen silicone oil, platinum catalyst and 1- acetenyl -1- cyclohexanol, at 25~35 DEG C mix
Uniformly, in 100~150 DEG C of sulfidization moldings, halogen-free flameproof enhancing add-on type liquid silicon rubber is obtained；
In terms of mass fraction, composition of raw materials component is：
The fire retardant is hindered amine intercalation modifying phosphoric acid hydrogen zirconium, and chemical formula is：
Wherein, the structural formula of X such as following formula：
R is H, CH3、C2H5、CH3- O or C2H5-O；I is 1 or 2.
Further to realize the object of the invention, it is preferable that the fire retardant is prepared via a method which：By 1 mass parts
Phosphoric acid hydrogen zirconium is dispersed in the second solvent of 30~100 mass parts, is subsequently adding hindered amine compound, ultrasonically treated 0.1~2h,
And 3~12h is stirred at 25~35 DEG C, by washing, centrifugation, drying obtains the hindered amine intercalation modifying phosphoric acid hydrogen
Zirconium；Second solvent is toluene, acetone or alcohol；The phosphoric acid hydrogen zirconium is 1 with the mol ratio of hindered amine compound:2~2:
1。
In si-h bond and vinyl silicone oil and hindered amine intercalation modifying phosphoric acid hydrogen zirconium (M-ZrP) in the containing hydrogen silicone oil
The mol ratio of carbon-carbon double bond summation is 1.5:1~2:1.Viscosity is 1000~20000mPa.s during 25 DEG C of the vinyl silicone oil.
Toluene and the mass ratio of hindered amine intercalation modifying phosphoric acid hydrogen zirconium are 30 in step b:1~100:1；Vinyl silicone oil with
The mass ratio of hindered amine intercalation modifying phosphoric acid hydrogen zirconium is 1:1~10:1.
The grinding is ground by three-roller.
A kind of halogen-free flameproof enhancing add-on type liquid silicon rubber, is obtained by above-mentioned preparation method.
Compared with prior art, the present invention has the following advantages：
1st, instant invention overcomes the shortcoming that inorganic combustion inhibitor addition is big, added in add-on type liquid silicon rubber it is a small amount of (<
5 mass parts) hindered amine intercalation modifying phosphoric acid hydrogen zirconium (M-ZrP), vertical combustion is that can reach UL-94V-0 grades.
2nd, the fire retardant prepared by the present invention contains carbon-carbon double bond, in sulfidation, by hydrosilylation and addition
Type liquid silastic forces mutual tolerance so that M-ZrP is dispersed in silicon rubber, and the P-OH on M-ZrP surfaces can be with
Hydrogen bond is generated with the oxygen atom in-Si-O-Si-, the mechanical property of silicon rubber is effectively improved.
3rd, halogen-free flameproof enhancing add-on type liquid silicon rubber of the invention has processing characteristics good, and curability is by fire-retardant
Noxious material and irritative gas are not discharged in the advantages of influence of agent is small, and combustion process, meets environmental requirement, can used extensively
In fields such as space flight and aviation, electronic apparatus and electric power.
Brief description of the drawings
Fig. 1 is the XRD spectra of ZrP and M-ZrP in embodiment 1.
Specific embodiment
To more fully understand the present invention, with reference to embodiment, the present invention is further illustrated, but of the invention
Implementation method not limited to this.
Performance characterization method in example below：
1st, the vulcanization characteristics of silicon rubber is determined according to GB/T 16584-1996.
2nd, the tensile strength and elongation at break of silicon rubber are determined according to GB/T 528-2009.
3rd, the tearing strength of silicon rubber is determined according to GB/T 529-2008.
4th, the Shore A hardness of silicon rubber is determined according to GB/T 531-2008
5th, fire resistance test：Limited oxygen index (LOI) performs test, specimen size according to GB/T 2406-1993 standards
It is 120mm × 10mm × 4mm；Vertical combustion (UL-94) performs test according to ASTM D635 standards, specimen size be 127mm ×
12.7mm×4mm。
Embodiment 1
By 6g phosphoric acid hydrogen zirconium (ZrP) add 600g toluene in, ultrasonic disperse 0.1h, add hindered amine 1 (phosphoric acid hydrogen zirconium with receive
Hinder the mol ratio 1 of amine 1:2), ultrasonically treated 0.5h, and 3h is stirred at 30 DEG C, washing, centrifugation, drying obtain hindered amine
Intercalation modifying phosphoric acid hydrogen zirconium (M-ZrP), the structural formula of hindered amine 1 is as follows.
From the XRD spectra (Fig. 1) of ZrP and M-ZrP, the interlamellar spacing of intercalation modifying phosphoric acid hydrogen zirconium (M-ZrP) of hindered amine 1
1.66nm (2 θ=5.26 °) is increased to by the 0.76nm (2 θ=11.64 °) of ZrP, shows that hindered amine 1 is successively inserted into ZrP interlayers.
By 91g vinyl silicone oils (viscosity 20000mPas, contents of ethylene 0.12wt% at 25 DEG C), 40g gas-phase silicas (ratio
Surface area is 360m2/ g) mix in vacuum kneader, 2h is kneaded at 30 DEG C, it is heated to 170 DEG C of temperature of charge and continues to knead
2h, then pumping vacuum and mixing 1h, grind after cooling through three-roller, obtain component A.
Take in 4.5g M-ZrP addition 250g toluene, ultrasonic disperse 0.5h adds 9g ethene silicone oil (in 25 DEG C of viscosity
20000mPas, contents of ethylene 0.12wt%), 2h is stirred at 30 DEG C, revolving removes toluene, obtains component B.
By above-mentioned component A and component B, 4.96g containing hydrogen silicone oil (hydrogen content 0.5wt%), 0.01g 1- acetenyl -1- rings
The divinyl tetramethyl disiloxane complex compound (platinum content 3000ppm) of hexanol and 0.25g chloroplatinic acids, the electricity consumption at 30 DEG C
Dynamic mixer is well mixed, and 10min is vulcanized at 120 DEG C, is made the thick films of 2mm and 4mm, and mechanical property and resistance are carried out respectively
Combustion performance test, as a result as shown in Table 1 and Table 2.
As can be seen from Table 1 and Table 2, the LOI of the add-on type liquid silicon rubber for being not added with M-ZrP in comparative example 1 is
28.0%, vertical combustion performance cannot be by UL-94 grades.And after adding 4.5g M-ZrP, the LOI of flame-proof silicon rubber from
28.0% rises to 31.0%, and vertical combustion performance shows that M-ZrP can significantly increase add-on type by UL-94V-0 grades
The fire resistance of liquid silastic.4.5g M-ZrP, the cure time T of flame-proof silicon rubber are added in addition90Extended to from 119s
156s, shows that M-ZrP can extend the cure time of add-on type liquid silicon rubber, but influence is little.By the mechanical property number in table 1
According to it can be found that the tensile strength of flame-proof silicon rubber increases to 8.36MPa from 7.93MPa, tearing strength increases from 20.60kN/m
To 26.03kN/m, show that M-ZrP can significantly improve the mechanical property of add-on type liquid silicon rubber.
Embodiment 2
By 6g phosphoric acid hydrogen zirconium (ZrP) add 180g acetone in, ultrasonic disperse 0.1h, add hindered amine 2 (phosphoric acid hydrogen zirconium with receive
Hinder the mol ratio 1 of amine 2:2), ultrasonically treated 2h, and 6h is stirred at 30 DEG C, washing, centrifugation, drying obtain hindered amine and insert
Layer modified phosphate hydrogen zirconium (M-ZrP), the structural formula of hindered amine 2 is as follows, and XRD results show that hindered amine 2 is successively inserted into phosphoric acid
Between hydrogen zirconium layer.
91g vinyl silicone oils (viscosity 20000mPas, contents of ethylene 0.12wt% at 25 DEG C), 40g gas phases is white
(specific surface area is 360m to carbon black2/ g) mix in vacuum kneader, 2h is kneaded at 30 DEG C, it is heated to 170 DEG C of temperature of charge
Continue to knead 2h, then pumping vacuum and mixing 1h, ground through three-roller after cooling, obtain component A.
Take in 4.5g M-ZrP addition 135g dimethyl ether, ultrasonic disperse 2h adds 9g ethene silicone oil (in 25 DEG C of viscosity
20000mPas, contents of ethylene 0.12wt%), 6h is stirred at 30 DEG C, revolving removes dimethyl ether, obtains component B.
By above-mentioned component A and component B, 4.96g containing hydrogen silicone oil (hydrogen content 0.5wt%), 0.01g 1- acetenyl -1- rings
The divinyl tetramethyl disiloxane complex compound (platinum content 3000ppm) of hexanol and 0.25g chloroplatinic acids, the electricity consumption at 30 DEG C
Dynamic mixer is well mixed, and 10min is vulcanized at 120 DEG C, is made the thick films of 2mm and 4mm, and mechanical property and resistance are carried out respectively
Combustion performance test, as a result as shown in Table 1 and Table 2.
Knowable to Tables 1 and 2, compared with Example 1, with the intercalation modifying phosphoric acid hydrogen zirconium of hindered amine 2, flame-proof silicon rubber is same
With preferable fire resistance and mechanical property, its LOI is 30.5%, and vertical combustion performance passes through UL-94V-0 grades；Stretching
Intensity is 8.56MPa, and tearing strength is 25.87kN/m.
Embodiment 3
By 6g phosphoric acid hydrogen zirconium (ZrP) add 300g ethanol in, ultrasonic disperse 0.1h, add hindered amine 3 (phosphoric acid hydrogen zirconium with receive
Hinder the mol ratio 1 of amine 3:2), ultrasonically treated 1h, and 6h is stirred at 30 DEG C, washing, centrifugation, drying obtain hindered amine and insert
Layer modified phosphate hydrogen zirconium (M-ZrP), the structural formula of hindered amine 3 is as follows, and XRD results show that hindered amine 3 is successively inserted into phosphoric acid
Between hydrogen zirconium layer.
91g vinyl silicone oils (viscosity 20000mPas, contents of ethylene 0.12wt% at 25 DEG C), 40g gas phases is white
(specific surface area is 360m to carbon black2/ g) mix in vacuum kneader, 2h is kneaded at 30 DEG C, it is heated to 170 DEG C of temperature of charge
Continue to knead 2h, then pumping vacuum and mixing 1h, ground through three-roller after cooling, obtain component A.
Take in 4.5g M-ZrP addition 450g carbon tetrachloride, ultrasonic disperse 2h adds 9g ethene silicone oil (in 25 DEG C glue
Degree 20000mPas, contents of ethylene 0.12wt%), 6h is stirred at 30 DEG C, revolving removes carbon tetrachloride, obtains component B.
By above-mentioned component A and component B, 4.96g containing hydrogen silicone oil (hydrogen content 0.5wt%), 0.01g 1- acetenyl -1- rings
The divinyl tetramethyl disiloxane complex compound (platinum content 3000ppm) of hexanol and 0.25g chloroplatinic acids, the electricity consumption at 30 DEG C
Dynamic mixer is well mixed, and 10min is vulcanized at 120 DEG C, is made the thick films of 2mm and 4mm, and mechanical property and resistance are carried out respectively
Combustion performance test, as a result as shown in Table 1 and Table 2.
Knowable to Tables 1 and 2, compared with Example 1, with the intercalation modifying phosphoric acid hydrogen zirconium of hindered amine 3, flame-proof silicon rubber is same
With preferable fire resistance and mechanical property, its LOI is 31.0%, and vertical combustion performance passes through UL-94V-0 grades；Stretching
Intensity is 8.41MPa, and tearing strength is 25.93kN/m.
Embodiment 4
The present embodiment difference from Example 1 is the mol ratio by phosphoric acid hydrogen zirconium and hindered amine 1 by 1:2 are changed into 2:1, phase
Corresponding containing hydrogen silicone oil consumption is changed into 3.23g from 4.96g.Knowable to Tables 1 and 2, the LOI of the flame-proof silicon rubber of the present embodiment can
To reach 29.5%, vertical combustion performance by UL-94V-0 grades, tensile strength and tearing strength be respectively 8.09MPa and
21.33kN/m, fire resistance and mechanical property compared with flame-proof silicon rubber in embodiment 1 have all declined, show phosphoric acid hydrogen zirconium with
The mol ratio of hindered amine 1 has a certain impact to the fire resistance and mechanical property of add-on type liquid silicon rubber.
Embodiment 5
The present embodiment difference from Example 1 is that containing hydrogen silicone oil consumption is reduced into 4.55g from 4.96g.By the He of table 1
Table 2 understands that the flame-proof silicon rubber LOI of the present embodiment is 29.5%, and vertical combustion performance is UL-94V-0 grades, cure time T90
Up to 258s, its tensile strength and tearing strength are respectively 8.03MPa and 21.73kN/m, compared with flame-proof silicon rubber in embodiment 1
Fire resistance and mechanical property have declined, and show fire resistance, vulcanization of the containing hydrogen silicone oil consumption to add-on type liquid silicon rubber
Performance and mechanical property have a certain impact.
Embodiment 6
The present embodiment difference from Example 1 is that M-ZrP consumptions are dropped into 2.5g, corresponding scattered second from 4.5g
Alkenyl silicon oil dosage is changed into 5.0g from 9.0g, and corresponding containing hydrogen silicone oil consumption is changed into 3.43g from 4.96g.From Tables 1 and 2,
Addition 2.5g M-ZrP, the LOI of add-on type liquid silicon rubber is 29.5%, and vertical combustion performance is UL-94V-0, tensile strength
8.13MPa and 24.16kN/m are respectively with tearing strength, show to add M-ZrP within the specific limits, flame-proof silicon rubber all has
Good fire resistance and mechanical property.
Embodiment 7
The present embodiment difference from Example 1 is that in the preparation process of component B, vinyl silicone oil consumption subtracts from 9g
4.5g is arrived less.From Tables 1 and 2, the LOI of the flame-proof silicon rubber of the present embodiment is 30.0%, and vertical combustion performance passes through UL-
94V-0 grades；Compared with Example 1, the flame-proof silicon rubber tensile strength of the present embodiment drops to 8.06MPa from 8.36MPa, tears
Resistance to spalling drops to 22.14kN/m from 26.03kN/m, shows in the preparation process of component B, reduces vinyl silicone oil consumption meeting
The fire resistance and mechanical property of add-on type liquid silicon rubber are reduced, this is probably that can cause due to reducing vinyl silicone oil consumption
M-ZrP disperses dispersiveness variation that is uneven and causing M-ZrP in silicon rubber in component B.
Embodiment 8
The present embodiment difference from Example 1 is that the medium vinyl silicone oil of embodiment 1 is changed into contents of ethylene to be
0.23wt%, viscosity are the vinyl silicone oil of 2000mPas (25 DEG C), and corresponding containing hydrogen silicone oil consumption increases to from 4.96g
6.34g.From Tables 1 and 2, the LOI of the flame-proof silicon rubber of the present embodiment is 30.5%, and vertical combustion performance passes through UL-
94V-0 grades；Compared with comparative example 2, the tensile strength of the flame-proof silicon rubber of the present embodiment increases to 5.79MPa from 5.10MPa,
Tearing strength increases to 12.14kN/m from 10.40kN/m, shows the vinyl silicone oil for different molecular weight, adds M-ZrP,
Add-on type liquid silicon rubber equally has good fire resistance and mechanical property.
Comparative example 1
By 100g vinyl silicone oils (viscosity at 25 DEG C is 20000mPas, and contents of ethylene is 0.12wt%),
(specific surface area is 360m to 40g fume colloidal silicas2/ g) mix in vacuum kneader, 2h is kneaded at 30 DEG C, it is heated to thing
170 DEG C of mixing 2h of material temperature degree, then pumping vacuum and mixing 1h, grind after cooling through three-roller, obtain component A；
By 1.51g containing hydrogen silicone oils (hydrogen content is 0.5wt%), 0.01g 1- acetenyl -1- cyclohexanol and 0.25g chloroplatinic acids
Divinyl tetramethyl disiloxane complex compound (platinum content is 3000ppm) add above-mentioned component A, stir at 30 DEG C
Uniformly, vulcanize 10min at 120 DEG C, be made the thick films of 2mm and 4mm, mechanical property and fire resistance test are carried out respectively,
Result is as shown in Table 1 and Table 2.
Comparative example 2
By 100g vinyl silicone oils (viscosity at 25 DEG C is 2000mPas, and contents of ethylene is 0.23wt%), 40g
(specific surface area is 360m to fume colloidal silica2/ g) mix in vacuum kneader, 2h is kneaded at 30 DEG C, it is heated to material temperature
170 DEG C of mixing 2h of degree, then pumping vacuum and mixing 1h, grind after cooling through three-roller, obtain component A；
By 2.89g containing hydrogen silicone oils (hydrogen content is 0.5wt%), 0.01g 1- acetenyl -1- cyclohexanol and 0.25g chloroplatinic acids
Divinyl tetramethyl disiloxane complex compound (platinum content is 3000ppm) add above-mentioned component A, stir at 30 DEG C
Uniformly, vulcanize 10min at 120 DEG C, be made the thick films of 2mm and 4mm, mechanical property and fire resistance test are carried out respectively,
Result is as shown in Table 1 and Table 2.
The curability and mechanical property of the add-on type liquid silicon rubber of table 1
The fire resistance of the add-on type liquid silicon rubber of table 2
Claims (7)
1. a kind of halogen-free flameproof strengthens the preparation method of add-on type liquid silicon rubber, it is characterised in that comprise the following steps：
A, the 55wt%~95wt% and gas-phase silica of raw material medium vinyl silicone oil are mixed in vacuum kneader, 25~
1~3h is kneaded at 35 DEG C, 140~180 DEG C of temperature of charge is heated to and is continued to knead 1~2h, then 0.5~1h of vacuum kneading, cooling
After grind, obtain component A；
B, by fire retardant ultrasonic disperse in the first solvent, ultrasonic time be 0.1~2h, add formula in remaining vinyl
Silicone oil, stirs 0.5~6h at 25~35 DEG C, and revolving removes the first solvent, obtains component B；First solvent be toluene,
Benzene, dimethyl ether, methyl ethyl ketone or carbon tetrachloride；
C, by component A, component B, containing hydrogen silicone oil, platinum catalyst and 1- acetenyl -1- cyclohexanol, mix equal at 25~35 DEG C
It is even, in 100~150 DEG C of sulfidization moldings, obtain halogen-free flameproof enhancing add-on type liquid silicon rubber；
In terms of mass fraction, composition of raw materials component is：
The fire retardant is hindered amine intercalation modifying phosphoric acid hydrogen zirconium, and chemical formula is：
Wherein, the structural formula of X such as following formula：
R is H, CH3、C2H5、CH3- O or C2H5-O；I is 1 or 2.
2. halogen-free flameproof according to claim 1 strengthens the preparation method of add-on type liquid silicon rubber, it is characterised in that institute
Fire retardant is stated to be prepared via a method which：The phosphoric acid hydrogen zirconium of 1 mass parts is dispersed in the second solvent of 30~100 mass parts,
Hindered amine compound, ultrasonically treated 0.1~2h are subsequently adding, and 3~12h is stirred at 25~35 DEG C, by washing, centrifugation point
From drying obtains the hindered amine intercalation modifying phosphoric acid hydrogen zirconium；Second solvent is toluene, acetone or alcohol；The phosphoric acid
Hydrogen zirconium is 1 with the mol ratio of hindered amine compound:2~2:1.
3. halogen-free flameproof according to claim 1 strengthens the preparation method of add-on type liquid silicon rubber, it is characterised in that institute
State rubbing for the carbon-carbon double bond summation in si-h bond in containing hydrogen silicone oil and vinyl silicone oil and hindered amine intercalation modifying phosphoric acid hydrogen zirconium
You are than being 1.5:1~2:1.
4. halogen-free flameproof according to claim 1 strengthens the preparation method of add-on type liquid silicon rubber, it is characterised in that institute
Viscosity is 1000~20000mPa.s when stating 25 DEG C of vinyl silicone oil.
5. halogen-free flameproof according to claim 1 strengthens the preparation method of add-on type liquid silicon rubber, it is characterised in that：Step
Toluene and the mass ratio of hindered amine intercalation modifying phosphoric acid hydrogen zirconium are 30 in rapid b:1~100:1；Vinyl silicone oil and hindered amine intercalation
The mass ratio of modified phosphate hydrogen zirconium is 1:1~10:1.
6. halogen-free flameproof according to claim 1 strengthens the preparation method of add-on type liquid silicon rubber, it is characterised in that institute
Grinding is stated to be ground by three-roller.
7. a kind of halogen-free flameproof enhancing add-on type liquid silicon rubber, it is characterised in that it is as described in claim any one of 1-6
Preparation method is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510007060.0A CN104774474B (en) | 2015-01-04 | 2015-01-04 | A kind of halogen-free flameproof enhancing add-on type liquid silicon rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510007060.0A CN104774474B (en) | 2015-01-04 | 2015-01-04 | A kind of halogen-free flameproof enhancing add-on type liquid silicon rubber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104774474A CN104774474A (en) | 2015-07-15 |
| CN104774474B true CN104774474B (en) | 2017-06-20 |
Family
ID=53616261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510007060.0A Active CN104774474B (en) | 2015-01-04 | 2015-01-04 | A kind of halogen-free flameproof enhancing add-on type liquid silicon rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104774474B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117605B (en) * | 2016-07-25 | 2019-05-14 | 华南理工大学 | A kind of in-situ inserted modified zirconium phosphate and preparation method thereof with flame-retardant smoke inhibition effect |
| CN109054728B (en) * | 2018-07-12 | 2021-07-06 | 佛山市方普防护技术有限公司 | Liquid silicone rubber impregnation liquid for copper bar insulation sheath and impregnation processing technology thereof |
| CN109369958B (en) * | 2018-12-14 | 2020-11-20 | 广东省稀有金属研究所 | Preparation method and application of organically modified zirconium phosphate |
| CN110845850B (en) * | 2019-11-07 | 2020-10-27 | 华南理工大学 | Ceramizable halogen-free flame-retardant silicone rubber and preparation method thereof |
| CN110845779B (en) * | 2019-11-14 | 2022-07-15 | 上海东方雨虹防水技术有限责任公司 | Modified composite flame-retardant TPO resin and preparation method thereof |
| CN113355047B (en) * | 2021-06-25 | 2022-08-02 | 上海珏晟新材料科技有限公司 | Flame-retardant liquid silica gel for bonding electrical elements and preparation method thereof |
| CN115491038A (en) * | 2022-09-16 | 2022-12-20 | 广州市矽友新材料科技有限公司 | Halogen-free platinum flame retardant for silicone rubber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706912A (en) * | 2005-04-26 | 2005-12-14 | 华南理工大学 | Phosphosilicate containing fire retardant and its prepn process |
| CN101735619A (en) * | 2009-12-28 | 2010-06-16 | 华南理工大学 | Halogen-free flame-retarded heat-conducting organic silicon electronic potting adhesive and preparation method thereof |
| CN102827452A (en) * | 2012-09-14 | 2012-12-19 | 天津金发新材料有限公司 | Flame retardant acrylonitrile butadiene styrene (ABS) composition with high heat resistance and high toughness and preparation method and application thereof |
| CN103724946A (en) * | 2013-12-19 | 2014-04-16 | 广州凯恒科塑有限公司 | Thermoplastic polyester elastomer heat-shrinkable casing tube for automobile wire harness as well as preparation method and application of heat-shrinkable casing tube |
| CN104231266A (en) * | 2014-08-22 | 2014-12-24 | 华南理工大学 | Macromolecular expansion type flame retardant containing hindered amine structure and preparation method and application of macromolecular expansion type flame retardant |
-
2015
- 2015-01-04 CN CN201510007060.0A patent/CN104774474B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706912A (en) * | 2005-04-26 | 2005-12-14 | 华南理工大学 | Phosphosilicate containing fire retardant and its prepn process |
| CN101735619A (en) * | 2009-12-28 | 2010-06-16 | 华南理工大学 | Halogen-free flame-retarded heat-conducting organic silicon electronic potting adhesive and preparation method thereof |
| CN102827452A (en) * | 2012-09-14 | 2012-12-19 | 天津金发新材料有限公司 | Flame retardant acrylonitrile butadiene styrene (ABS) composition with high heat resistance and high toughness and preparation method and application thereof |
| CN103724946A (en) * | 2013-12-19 | 2014-04-16 | 广州凯恒科塑有限公司 | Thermoplastic polyester elastomer heat-shrinkable casing tube for automobile wire harness as well as preparation method and application of heat-shrinkable casing tube |
| CN104231266A (en) * | 2014-08-22 | 2014-12-24 | 华南理工大学 | Macromolecular expansion type flame retardant containing hindered amine structure and preparation method and application of macromolecular expansion type flame retardant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104774474A (en) | 2015-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104774474B (en) | A kind of halogen-free flameproof enhancing add-on type liquid silicon rubber and preparation method thereof | |
| Feng et al. | Multi-functional interface tailoring for enhancing thermal conductivity, flame retardancy and dynamic mechanical property of epoxy/Al2O3 composites | |
| CN104974530B (en) | A kind of high-performance anti creepage trace silicon rubber and preparation method thereof | |
| Wang et al. | Preparation of silane precursor microencapsulated intumescent flame retardant and its enhancement on the properties of ethylene–vinyl acetate copolymer cable | |
| JP5795840B2 (en) | Silica particle material, silica particle material-containing composition, and silica particle surface treatment method | |
| CN107129689B (en) | High-performance anti creepage trace add-on type liquid silicon rubber composition and preparation method thereof | |
| CN101381584B (en) | Modified organosilicon solvent-free dip varnish and preparation method thereof | |
| DD157104A5 (en) | SILICONEMASSE | |
| CN101735619A (en) | Halogen-free flame-retarded heat-conducting organic silicon electronic potting adhesive and preparation method thereof | |
| WO2013076036A1 (en) | Composition of olefinically functionalsied siloxane oligomers based on alkoxy silanes | |
| CN103694709B (en) | Add-on type liquid silicon rubber anti creepage trace agent and its preparation method and application | |
| CN106118068A (en) | A kind of flame-resistant high-temperature-resistant electrically insulating silicone rubber compositions and preparation method thereof | |
| Cabrera‐Alvarez et al. | Study of the silane modification of magnesium hydroxide and their effects on the flame retardant and tensile properties of high density polyethylene nanocomposites | |
| EP3608384A1 (en) | Heat-conductive sheet | |
| Zhang et al. | Significant improvement of urethane-containing silane on the tracking and erosion resistance of silicone rubber/silica nanocomposite by enhancing the interfacial effect | |
| CN107936572A (en) | A kind of high transparency heat oxygen aging resistance add-on type liquid silicon rubber and preparation method thereof | |
| CN106674599B (en) | The preparation method and application of silicon rubber functionalization graphene | |
| Zhang et al. | Suppression effect and mechanism of amine-containing MQ silicone resin on the tracking and erosion resistance of silicone rubber | |
| CN101821818A (en) | Surface modified electrical insulation system with improved tracking and erosion resistance | |
| CN115838496A (en) | Preparation method and application of organic-inorganic hybrid carbonizing agent of polyphosphazene modified titanium carbide nanosheet | |
| CN102775795A (en) | Peroxide vulcanized rubber | |
| CN110669471A (en) | Environment-friendly high-strength organic silicon adhesive and preparation method thereof | |
| CN107474731A (en) | A kind of high-temperature resistant coating containing modified graphene and preparation method thereof | |
| TWI447174B (en) | Flammable organic polysiloxane composition | |
| EP2354145A1 (en) | Use of polyorganosiloxanes in processing and vulcanising rubber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| OL01 | Intention to license declared | ||
| OL01 | Intention to license declared |